CN111093457A - Household appliance with a component part comprising an anchored polyoxometalate, method for producing a polyoxometalate and method for producing the component part - Google Patents
Household appliance with a component part comprising an anchored polyoxometalate, method for producing a polyoxometalate and method for producing the component part Download PDFInfo
- Publication number
- CN111093457A CN111093457A CN201880060424.3A CN201880060424A CN111093457A CN 111093457 A CN111093457 A CN 111093457A CN 201880060424 A CN201880060424 A CN 201880060424A CN 111093457 A CN111093457 A CN 111093457A
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- CN
- China
- Prior art keywords
- polyoxometalate
- household appliance
- anchored
- cations
- positive charge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000013460 polyoxometalate Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- -1 quaternary ammonium cations Chemical class 0.000 claims description 83
- 150000001768 cations Chemical class 0.000 claims description 78
- 229910052698 phosphorus Inorganic materials 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 229910052710 silicon Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 150000001450 anions Chemical class 0.000 claims description 33
- 229910052796 boron Inorganic materials 0.000 claims description 29
- 229910052732 germanium Inorganic materials 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 229910052720 vanadium Inorganic materials 0.000 claims description 28
- 229910052804 chromium Inorganic materials 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000004743 Polypropylene Substances 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
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- 239000011521 glass Substances 0.000 claims description 12
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- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
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- 239000002344 surface layer Substances 0.000 claims description 6
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- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000010936 titanium Substances 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
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- 150000001875 compounds Chemical class 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000010797 grey water Substances 0.000 description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
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Images
Classifications
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- B01J35/39—
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
- D06F35/005—Methods for washing, rinsing or spin-drying
- D06F35/008—Methods for washing, rinsing or spin-drying for disinfecting the tub or the drum
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/4236—Arrangements to sterilize or disinfect dishes or washing liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/006—Recovery arrangements, e.g. for the recovery of energy or water
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- D06F39/20—
Abstract
The invention relates to a household appliance (1) having a component part (12, 18) comprising a polymer and at least one polyoxometalate, wherein the polyoxometalate is anchored to a silica-containing matrix. The invention further relates to a method for producing polyoxometallates anchored to a silicon dioxide-containing substrate, and to a method for producing the component parts (12, 18).
Description
Technical Field
The invention relates to a household appliance having a component part comprising a polymer and a polyoxometalate, to a process for manufacturing the polyoxometalate for use therein and to a process for manufacturing the component part.
Background
The household appliance may come into contact with dust, dirt, food, or moisture, or may be touched by animals or during use. Therefore, problems related to hygiene may be caused by microorganisms that attach to and proliferate in home appliances. In particular, a contaminated and hygienically objectionable household appliance or at least a household appliance with discoloration may result. In the worst case this may even be a health hazard. It is therefore recommended to clean the household appliance regularly. However, the convenience and effectiveness of such cleaning can be determined by the type and amount of contamination. In some cases, a biofilm may form or has already formed. Biofilms composed of organic matter such as microorganisms and nutrients can cause malodour and/or visible contamination.
This is particularly true of household appliances that come into contact with food stored, processed or prepared inside the household appliance. In addition, vacuum cleaners are also susceptible to microbial contamination.
Generally, articles that have been soiled in various ways are cleaned in a water-containing running household appliance. Food residues can occur in dishwashers and the range of soils occurring in the laundry to be cleaned in a washing machine is generally greater. Common to all water-containing domestic appliances is that dirt is produced and accumulates in moist and warm environments, in particular in places which are difficult to access. This fouling may be a good nutrient medium for organisms such as bacteria or fungi.
A general problem with domestic appliances is that microorganisms tend to grow faster and easier in a humid environment, especially in less ventilated places, which are also often less accessible. For example, condensed water in a refrigerator may promote the growth of microorganisms. Containers for liquids such as water and milk, for example in coffee machines, are prone to microbial production.
It is therefore desirable to provide a household appliance which can be operated more hygienically and which can take measures to avoid biofilm formation.
Various measures for removing and/or preventing biofilms are known from the prior art. A machine cleaning program is provided which removes accumulated dirt at high temperatures with the aid of detergent and sometimes with increased liquid level and/or with increased drum rotation speed, i.e. with increased mechanical energy input. It is also known to use ozone to remove organic foulants.
Methods have also previously been proposed for removing organic fouling by means of UV-C radiators using the through-flow principle, in such a way that the microorganisms in these fouling are killed by destroying their genetic material.
In the most known method, it is envisaged to use an antimicrobial active ingredient, such as silver ions, in the surface of a domestic appliance. However, a disadvantage of these components is that they are gradually removed from the surface and thus become depleted. In addition, when Ag+Or Cu+Ions also have a detrimental effect on groundwater and water circuit contamination when used in water-carrying domestic appliances, for example in the washing liquid and on the surface of materials in contact with the washing liquid. However, if these active ingredients are not washed out of the carrier material of the surface of the household appliance, their efficacy is mostly so small that in the long term, microorganisms and even biofilms form on the surface and have a negative effect on the hygiene of the household appliance and generate odors.
Photocatalytic processes are known, for example using catalytically acting compounds, in particular titanium dioxide coatings for deodorization, disinfection and cleaning. Therefore, the catalyst needs to be activated often by means of UV radiation. These compounds support oxidative modification or destruction of microorganisms so that they are removed in their entirety by oxidation in the best case. However, this method generally does not work sufficiently, in particular UV light is additionally required for the oxidation.
The disadvantage of these known methods and measures is the high energy consumption and sometimes high equipment and/or operating costs for achieving a significant effect. In some methods, health-hazardous agents are used, such as ozone or violet UV radiation, requiring additional safety measures.
The use of polyoxometalates in various fields is well known, for example in analytical and clinical chemistry, catalysis (including photocatalysis), biochemistry (inhibition of electron transfer processes), medicine (anti-tumour and anti-viral activity) and the manufacture of integrated circuits.
Publication DE 102009026712 a1 discloses a household appliance having at least one component, the surface of which may be affected by organic soiling, said surface being provided with a photocatalyst, a light source for irradiating said photocatalyst with activating electromagnetic radiation being associated with said surface, said surface being formed of a preliminarily formed first material in which the photocatalyst is dispersed. Materials having titanium dioxide and modifications thereof are disclosed in great detail as photocatalysts.
Publications EP 2761073B 1 and US 2014/231363 a1 disclose a water-conducting household appliance having a container for receiving objects to be cleaned and at least one inner surface containing a catalytically active substance, which is arranged in the household appliance, wherein the catalytically active substance is a polyoxometalate. During operation of the household appliance, the inner surface is in contact with the water to be cleaned. Preferably, the polyoxometalate is a tungstate, and more preferably, the tungstate is modified with titanium.
The publications DE 102013205302 a1 and WO 2014/154432 a1 disclose a household appliance which comprises at least one catalytic substance on the surface, wherein the catalytic substance is a polyoxometalate contained in the inner and/or outer surface of the household appliance, which polyoxometalate is contained at least in the outer surface of the household appliance if the household appliance is a water-bearing running household appliance having a container for receiving an object to be cleaned.
Publication EP 1439261 a2 describes a polyoxometalate-modified fabric or an article comprising the polyoxometalate-modified fabric, which article comprises a fabric and at least one generalized polyoxometalate. Further, the use of the fabric for removing contaminants selected from the group consisting of aliphatic nitrogen compounds, sulfur compounds, halogenated compounds, and aliphatic oxygen compounds from the fabric is disclosed. Further disclosed is the use for removing microorganisms from a gas or liquid phase.
Publication WO 2015/0787737 a1 discloses a water-conducting household appliance having a storage tank for storing a quantity of greywater and a treatment device for treating the greywater stored in the storage tank. The water-bearing domestic appliance is configured for determining an amount of greywater stored in the storage tank and for operating the treatment device as a function of the determined amount of greywater stored in the storage tank.
Publication WO 2014/122225A 1 discloses the use of heteropolyoxometalates of the formula (I), (II) or (III)
Aq+3PVqZ12-qO40(I)，
A6P2Z18O62(II), or
A3PZ4O24(III)
Wherein Z is selected from Mo or W,
the index q is 0, 1, 2 or 3, and
a is selected from one or more cations and comprises at least one cation selected from the group consisting of quaternary ammonium cations, quaternary phosphonium cations and tertiary sulfonium cations for providing self-cleaning, exfoliating, disinfecting, self-disinfecting, biocidal, antimicrobial and/or deodorizing properties to at least a portion of a substrate or a surface of a substrate or to a coating, or for decomposition and/or degradation of organic materials. In formula (I), Z is preferably Mo and q ═ 2, and in formula (III), Z is preferably W.
Publication EP 2765136A 1 discloses heteropolyoxometalates of the formula (I), (II) or (III)
Aq+3PVqZl2-qO40(I)，
A6P2Z18O62(II), or
A3PZ4O24(III)
Wherein Z is selected from Mo or W,
q is 1, 2 or 3, and
a is selected from one or more than two cations and comprises at least one quaternary ammonium cation, with the proviso that the compound [ (n-C)4H9)4N]3PMo12O40And [ (n-C)6H9)4N]3PMo12O40Is dispensed with. Most preferred are heteroPolyoxometallate [ (n-C)4H9)4N]3PW4O24And [ (n-C)6H13)4N]3PW4O24。
However, the incorporation of polyoxometallates into polymers is difficult. Most commercial coating systems react with polyoxometallates, producing side effects if coating methods are used, such as component parts comprising coatings. This leads to degradation of the polyoxometallate or coating system. With the introduction of such polyoxometallates, the coating becomes brittle and can be easily removed from the polymer support, i.e. the polymer matrix. Most polyoxometalates that function as biocides degrade if a bulk process is used due to the harsh operating conditions required to process the polymer. For example, during injection molding of polypropylene, the minimum temperature for melting of polypropylene is 180 ℃ and the pressure is above atmospheric pressure. Experiments have shown that under these conditions 80% of the polyoxometallate used is degraded. Furthermore, the amount of polyoxometallate in the surface of the component part is generally too low to achieve effective antimicrobial use, since both methods can be tolerated and the percentage of polyoxometallate available in the surface of the component part is generally insufficient.
Disclosure of Invention
In view of this situation, it is an object of the present invention to provide a household appliance with improved hygiene, since a sufficient amount of polyoxometallate in the component parts can be established in a reliable manner. The polyoxometallate used therein should preferably not be readily degradable. In particular, there should also be less degradation during the manufacture of the domestic appliance, in particular during the manufacture of the component parts comprising these polyoxometallates. That is, the incorporation of Polyoxometallate (POM) into the part of the component containing the polymer should be improved.
According to the invention, this object is achieved by a household appliance, a process for manufacturing polyoxometallates for use therein and a process for manufacturing component parts according to the invention. In other respects, preferred embodiments of the household appliance are disclosed. Preferred embodiments of the household appliance correspond to preferred embodiments of the process for manufacturing the polyoxometallate used therein and to preferred embodiments of the process for manufacturing the component part, and vice versa, even if not explicitly stated herein.
The invention therefore relates to a household appliance, preferably a water-conducting household appliance, having a component part comprising a polymer, preferably a thermoplastic polymer, and at least one polyoxometalate, wherein the polyoxometalate is anchored on a silica-containing matrix.
The term "household appliance" as used herein refers to a device intended for private home applications, also including communication and data processing devices, which are adapted and intended to interact with the device for private home applications. In particular, the following domestic applications are included: stoves, ovens, baking ovens, microwaves, stove pans, range hoods, dishwashers, washing machines, clothes dryers, refrigerators, freezers, vacuum cleaners, coffee makers, water boilers, vegetable oil cookers, irons, hair dryers, shavers, kitchen machines and kitchen appliances, barbecue appliances, steam cookers, small instantaneous electric water heaters, appliances for heating and storing water for kitchens and bathrooms, and robotic applications, as long as they are intended for private home applications.
Accordingly, the term "component part" is to be understood broadly. Depending on the household appliance concerned, the shape and composition thereof may vary greatly.
The household appliance is preferably a water-conducting household appliance. Generally, a water-carrying home appliance is a home appliance that uses water during its operation. The items to be cleaned may in particular be dishes or laundry. According to the invention, cleaning is also understood to mean preservation. The water-bearing domestic appliance can therefore also be a clothes dryer.
In a preferred embodiment, the water-conducting household appliance is a dishwasher or a laundry treatment device or a coffee maker.
In another preferred embodiment, the water-carrying household appliance belongs to the group consisting of a washer, washer-dryer and dryer.
As referred to herein, the term "microorganism" includes bacteria, viruses, fungi, and algae. Preferably, as used herein, the term "microorganism" refers to a bacterium.
As used herein, the term "biofilm" refers to a collection of microorganisms in which cells adhere to each other in a household appliance or on a surface of a component part on a household appliance. As used herein, the term "growth of biofilm" or "biofilm growth" refers to the accumulation of microorganisms attached to the surface of a component part in or on a household appliance.
In a preferred household appliance, the silica-containing matrix is selected from the group consisting of silica minerals, aluminosilicate minerals and glass. The aluminosilicate mineral is preferably a zeolite. Furthermore, the glass is preferably in the form of hollow glass microspheres or glass fibers. Suitable hollow glass microspheres are, for example, hollow glass microspheres iM16K from 3M company.
The household appliance of the invention preferably comprises, as at least one polyoxometalate, a heteropolyoxometalate of formula (I), (II), (III), (IV) and/or (V):
[An]m+[XMqZr-q-oZ’oOs]m-(I)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
r is 11 or 12, and r is a linear or linear,
o is 0 or 1, or a combination thereof,
s-37, 38, 39 or 40,
when r is 11, q is 0, 1, 2,3, 4, 5, 6, 7, 8 or 9,
when r is 12, q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10, and
when r is 12, s is 40, X is P and q is 0, 1, 2 or 3, M is not V;
[An]m+[XMqZt-q-oZ’oO24]m-(II)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
t is 4 or 6, and the total weight of the product,
o is 0 or 1, or a combination thereof,
when t is 6, q is 0, 1, 2,3 or 4,
when t is 4, q is 0, 1 or 2, and
q is 1, 2 or 3 when t ═ 4 and X ═ P;
[An]m+[XpMqZ6-q-p-oZ’oOl9]m-(III)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
p is 0 or 1, and
q is 0, 1, 2 or 3,
when p is 0, M is not V;
[An]m+[X2MqZl8-q-oZ’oO62]m-(IV)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and
q is 1, 2 or 3 when X ═ P;
[An]m+[X5MqZ30-q-oZ’oO110]m-(V)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27;
and wherein A is selected from one or two or more cations and comprises at least one cation selected from the group consisting of quaternary ammonium cations, quaternary phosphonium cations and tertiary sulfonium cations.
In a preferred embodiment, the invention relates to a household appliance, wherein the polyoxometalate is a heteropolyoxometalate of formulae (I), (II), (III), (IV) and (V), wherein Z ═ W. Even more preferably, o ═ 0. Thus, more preferred polyoxometalates are the heteropolyoxometalates of the following formulae (I '), (II '), (III '), (IV ') and (V '):
[An]m+[XMqWr-qOs]m-(I’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
r is 11 or 12, and r is a linear or linear,
s-37, 38, 39 or 40,
when r is 11, q is 0, 1, 2,3, 4, 5, 6, 7, 8 or 9,
when r is 12, q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10, and
when r is 12, s is 40, X is P and q is 0, 1, 2 or 3, M is not V;
[An]m+[XMqWt-qO24]m-(II’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
t is 4 or 6, and the total weight of the product,
when t is 6, q is 0, 1, 2,3 or 4,
when t is 4, q is 0, 1 or 2, and
q is 1, 2 or 3 when t ═ 4 and X ═ P;
[An]m+[XpMqW6-q-pO19]m-(III’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
p is 0 or 1, and
q is 0, 1, 2 or 3, and
when p is 0, M is not V;
[An]m+[X2MqW18-qO62]m-(IV’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and
q is 1, 2 or 3 when X ═ P;
[An]m+[X5MqW30-qO110]m-(V’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27.
In formula (I'), r is preferably 12, s is preferably 40, and q is preferably 0, 1, 2 or 3, thereby producing formula [ An]m+(XMqW12- qO40)m-The heteropolyoxometalates of (a).
In formula (II'), q is preferably 0 when t ═ 6, thereby yielding formula [ a ═ an]m+[XW6O24]m-The heteropolyoxometalates of (a).
In formula (II'), q is preferably 0 when t ═ 4, thereby yielding formula [ a ═ an]m+[XW4O24]m-The heteropolyoxometalates of (a).
In formula (III'), p and q are preferably 0, thereby giving formula [ An]m+[W6O19]m-Polyoxometallate of (1).
In formula (IV'), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby producing formula [ An]m+[X2W18O62]m-The heteropolyoxometalates of (a).
In formula (V'), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby producing formula [ An]m+[X5W30O110]m-The heteropolyoxometalates of (a).
In another preferred embodiment, the present invention relates to the use as described herein of heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), wherein, in formulae (I), (II), (III), (IV) and (V), Z ═ Mo. In the case where o ═ 0, this embodiment encompasses heteropolyoxometalates of the following formulae (I "), (II"), (III "), (IV") and (V "):
[An]m+[XMqMor-qOs]m-(I”)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
r is 11 or 12, and r is a linear or linear,
s-37, 38, 39 or 40,
when r is 11, q is 0, 1, 2,3, 4, 5, 6, 7, 8 or 9,
when r is 12, q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10, and
when r is 12, s is 40, X is P and q is 0, 1, 2 or 3, M is not V;
[An]m+[XMqMOt-q-oO24]m-(II”)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
t is 4 or 6, and the total weight of the product,
when t is 6, q is 0, 1, 2,3 or 4,
when t is 4, q is 0, 1 or 2, and
q is 1, 2 or 3 when t ═ 4 and X ═ P;
[An]m+[XpMqMo6-q-pO19]m-(III”)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
p is 0 or 1, and
q is 0, 1, 2 or 3
When p is 0, M is not V;
[An]m+[X2MqMo18-qO62]m-(IV”)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and
q is 1, 2 or 3 when X ═ P;
[An]m+[X5MqMo30-qO110]m-(V”)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27.
In formula (I'), r is preferably 12, s is preferably 40, and q is preferably 0, 1, 2 or 3, resulting in formula [ An]m+[XMqMo12-qO40]m-The heteropolyoxometalates of (a).
In formula (II "), q is preferably 0 when t is 6, thereby yielding formula [ a ″n]m+[XMo6O24]m-The heteropolyoxometalates of (a).
In formula (II "), q is preferably 0 when t is 4, thereby yielding formula [ a ″n]m+[XMo4O24]m-The heteropolyoxometalates of (a).
In formula (III'), p and q are preferably 0, resulting in the formula [ An]m+[Mo6O19]m-Polyoxometallate of (1).
In formula (IV "), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby yielding formula [ An]m+[X2Mo18O62]m-The heteropolyoxometalates of (a).
In formula (V'), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby producing formula [ An]m+[X5Mo30O110]m-The heteropolyoxometalates of (a).
In another preferred embodiment, the present invention relates to the use as described herein of heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), wherein, in formulae (I), (II), (III), (IV) and (V), Z ═ W and Z '═ Mo and o ═ 1, thus encompassing heteropolyoxometalates of formulae (I' "), (II '"), (III' "), (IV '") and (V' "):
[An]m+[XMqWr-q-1MoOs]m-(I”’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
r is 11 or 12, and r is a linear or linear,
s-37, 38, 39 or 40,
when r is 11, q is 0, 1, 2,3, 4, 5, 6, 7, 8 or 9,
when r is 12, q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10, and
when r is 12, s is 40, X is P and q is 0, 1, 2 or 3, M is not V;
[An]m+[XMqWt-q-1MoO24]m-(II”’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
t is 4 or 6, and the total weight of the product,
when t is 6, q is 0, 1, 2,3 or 4,
when t is 4, q is 0, 1 or 2, and
q is 1, 2 or 3 when t ═ 4 and X ═ P;
[An]m+[XpMqW5-q-pMoO19]m-(III”’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
p is 0 or 1, and
q is 0, 1, 2 or 3;
[An]m+[X2MqW17-qMoO62]m-(IV”’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and
q is 1, 2 or 3 when X ═ P;
[An]m+[X5MqW29-qMoO110]m-(V”’)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27;
in formula (I '), r is preferably 12, s is preferably 40, and q is preferably 0, 1, 2 or 3, thereby yielding formula [ A' ]n]m+[XMqW11-qMoO40]m-The heteropolyoxometalates of (a).
In formula (II' "), q is preferably 0 when t ═ 6, thereby yielding formula [ a ″n]m+[XW5MoO24]m-The heteropolyoxometalates of (a).
In formula (II' "), q is preferably 0 when t ═ 4, thereby yielding formula [ a ″n]m+[XW3MoO24]m-The heteropolyoxometalates of (a).
In formula (III'), p and q are preferably 0, resulting in the formula [ An]m+[W5MoO19]m-Polyoxometallate of (1).
In formula (IV '"), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby yielding formula [ A' ]n]m+[X2W17MoO62]m-The heteropolyoxometalates of (a).
In formula (V '), q is preferably 0, 1, 2 or 3, and more preferably 0, thereby producing formula [ A' ]n]m+[X5W29MoO110]m-The heteropolyoxometalates of (a).
In another preferred embodiment of the household appliance, in the heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), X is selected from P, Si and Al. It is also preferred that in formulae (I '), (II '), (III '), (IV ') and (V '), X is selected from P, Si and Al. Furthermore, it is preferred that in formulae (I "), (II"), (III "), (IV") and (V "), X is selected from P, Si and Al. Furthermore, preferably in formulae (I ' "), (II '"), (III ' "), (IV '") and (V ' "), X is also selected from P, Si and Al.
Furthermore, in the present invention, it is preferred that in the heteropolyoxometalates of the formulae (I), (II), (III), (IV) and (V), in the heteropolyoxometalates of the formulae (I '), (II '), (III '), (IV ') and (V '), in the heteropolyoxometalates of the formulae (I '), (II '), (III '), (IV ') and (V ') and in the heteropolyoxometalates of the formulae (I '), (II '), (III '), (IV ') and (V '), M is selected from Co, Ti and V.
In a further preferred embodiment, the invention relates to a household appliance, wherein, in the heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), X ═ P or Si and M ═ V. It is also preferred that in formulae (I '), (II'), (III '), (IV') and (V '), in formulae (I "), (II"), (III "), (IV") and (V "), and in formulae (I'"), (II '"), (III'"), (IV '") and (V'"), X ═ P or Si and M ═ V.
In an alternative preferred embodiment, the invention relates to a household appliance, wherein, in the heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), X ═ P or Si and M ═ Ti. Furthermore, it is preferred that in formulae (I '), (II'), (III '), (IV') and (V '), (I "), (II"), (III "), (IV") and (V "), and in formulae (I'"), (II '"), (III'"), (IV '") and (V'"), X ═ P or Si and M ═ Ti.
In a further alternative preferred embodiment, the invention relates to a household appliance, wherein, in the heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V), X ═ P or Si and M ═ Co. Also preferred are in formulae (I '), (II '), (III '), (IV ') and (V '), X ═ P or Si and M ═ Co. Furthermore, it is preferred that in formula (I "), (II"), (III "), (IV") and (V "), and in formula (I '"), (II ' "), (III '"), (IV ' "), and (V '"), X ═ P or Si and M ═ Co.
In a further alternative preferred embodiment, the invention relates to a household appliance, wherein, in the heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V) and in formulae (I '), (II'), (III '), (IV') and (V '), in formulae (I "), (II"), (III "), (IV") and (V ") and in formulae (I'"), (II '"), (III'"), (IV '") and (V'"), X ═ Al and M ═ Co, V or Ti.
The particularly preferred heteropolyoxometalates which impart antimicrobial properties to the surface of the domestic appliance, wherein the surface is the surface of a component substrate in or on the domestic appliance, and which reduce, preferably inhibit, the growth of biofilms on the surface of the substrate in or on the domestic appliance are the following:
heteropolyoxometalates based on the formula (I): a. then[SiVW11O40]、An[SiV2W10O40]、An[SiV3W9O40]、An[SiV4W8O40]、An[SiVMo11O40]、An[SiV2Mo10O40]、An[SiV3Mo9O40]、An[SiV4Mo8O40]、An[PV6Mo6O40]、An([PV5Mo7O40]、An([PV8Mo4O40]、An[PCoW11O39]、An[AlVW11O40]、An[SiVW10MoO40]；
Heteropolyoxometalates based on the formula (II): a. then[PW6O24]、An[PMo6O24]、An[SiW6O24]、An[SiMo6O24]、An[AlW6O24]、An[AlMo6O24]、An[SiW4O24]、An[SiMo4O24]、An[AlW4O24]、An[AlMo4O24]；
Polyoxometallates based on formula (III): a. then[W6O19]And An[Mo6O19]；
Heteropolyoxometalates based on the formula (IV): a. then[Si2W18O62]、An[Si2Mo18O62]；
Heteropolyoxometalates based on the formula (V): a. then[P5W30O110]、An[Si5W30O110]、An[Al5W30O110]、An[P5Mo30O110],An[Si5Mo30O110]、An[Al5Mo30O110]。
In addition to the fact that the catalytic activity is primarily associated with transition metals, the modification of the entire molecule may also induce improved generation of Reactive Oxygen Species (ROS). Furthermore, depending on the end use application, these modifications may provide chemical or physical properties to the catalyst as desired without affecting the final performance as a catalyst. Thus, heteropolyoxometalates represent a promising family of compounds that is sufficiently mature. Their versatility is a result of their many structures, the ability to delocalize electrons over the surface of clusters, and the ability to introduce heteroanions, electrophiles, and ligands.
The heteropolyoxometalates described herein have been shown to have desirable properties useful for simultaneously imparting antimicrobial properties to the surface of a component part in or on a household appliance and reducing the growth of biofilm on the surface of a substrate in or on a household appliance. Heteropolyoxometalates as described herein typically consist of a cationic moiety [ A ] that confers antimicrobial activity to the compoundn]m+And heteropoly oxometallate anions. Heteropolyoxometalates exhibit flexible redox behaviour, which means that they can be usedOne or more electrons are reversibly reduced. In particular, it has been found that these heteropolyoxometalates have the ability to activate molecular oxygen and/or hydrogen peroxide, preferably molecular oxygen, when introduced into the component parts of a domestic appliance, which means that electrons are transferred from the heteropolyoxometalate to molecular oxygen and/or hydrogen peroxide, preferably molecular oxygen, leading to the formation of Reactive Oxygen Species (ROS), such as superoxide anions (O)2 -) And oxidized heteropolyoxometalate species.
The reactive oxygen species formed by activation of molecular oxygen and/or hydrogen peroxide, preferably molecular oxygen, induced by the heteropolyoxometalates reduce the growth of biofilm on the surface of substrates in or on household appliances comprising heteropolyoxometalates. Furthermore, this is useful for maintaining the antimicrobial activity of the matrix used in the household appliance, which is generated by the at least one heteropolyoxometalate comprised therein, over a long time scale.
The cationic portion of the oxidized heteropolyoxometalate species then reacts with the negatively charged cell membranes of the microorganisms, thereby killing the microorganisms, thereby resulting in antimicrobial activity of the heteropolyoxometalate and the portion of the component used in the household appliance comprising the heteropolyoxometalate, respectively.
Thus, the heteropolyoxometalates described herein provide a synergistic effect. They have antimicrobial properties because of their ability to react with the cell membrane of microorganisms and to generate Reactive Oxygen Species (ROS), in particular superoxide anions (O)2 -) The ability of the cell to perform. This reduces the growth of biofilm on the surface of component parts in or on household appliances comprising the heteropolyoxometalate, so that the antimicrobial activity of the substrate used in the household appliance can be maintained for a long period of time. Due to the anchoring of the heteropolyoxometalates on the silica-containing matrix, the heteropolyoxometalates are virtually stabilized in the component part, so that the antimicrobial action can be exerted over a long period of time.
It will be appreciated that the cation A is selected such that in the heteropolyoxometalates the charge of the compounds of formulae (I), (II), (III), (IV) and (V) is zero. To achieve this, the number and/or charge of the cations a may be varied and/or the charge may be balanced by one or more further cations and/or anions.
In general, polyoxometallates based on molybdenum (Mo) or tungsten (W) are well known in the art, in particular as Keggin-type polyoxometallate anions [ XZ12O40]n-Wherein the central heteroatom (X) may be, for example, phosphorus (P)5+) Silicon (Si)4+) Germanium (Ge)4+) Aluminum (Al)3+) Boron (B)3+) And the like. Further, in the Keggin-type polyoxometallate based on molybdenum or tungsten, a certain number (1 or more) of molybdenum or tungsten atoms may be replaced with titanium atoms (e.g., Ti4+) Vanadium atom (e.g. V)5+) Nickel atom (e.g. Ni)2+) Iron atom (e.g. Fe)3+) Cobalt atoms (e.g. Co)2+Or Co3+) Zinc atom (Zn)2+) Chromium atom (e.g. Cr)2+Or Cr3+) Manganese atom (e.g. Mn)2+) And so on.
Another example of polyoxometallate anions is the Wells-Dawson class [ X ]2Z18O62]n-. The heteropolyoxometalate anion comprises two heteroatoms (X), which may be, for example, phosphorus (P)5+) Silicon (Si)4+) Germanium (Ge)4+) Aluminum (Al)3+) Boron (B)3 +) And 18 molybdenum or tungsten atoms (Z). Furthermore, in the tungsten-based polyoxometallate of the Wells-Dawson type, one or more tungsten atoms may, for example, consist of vanadium atoms (e.g. V)5+) And (6) replacing.
Other well-known structures are the Ventrollo structure [ XZ4O24]nAnd Anderson structure [ XZ6O24]n-Wherein Z is tungsten (W)6+) Or molybdenum (Mo)6+) X is a heteroatom, e.g. phosphorus (P)5+)。
Formula [ Z ]6O19]n-Is called Lindquist structure, wherein Z is tungsten (W)6+) Or molybdenum (Mo)6+)。
Typically, these heteropoly oxometalate anions are inAre well known in the art, and it is known that the negative charge of anions is generally represented by Li+、Na+、K+Or NH4 +Such as, for example, cations, thereby providing solubility of the resulting salt in water.
It will be appreciated that in these materials, the cation A is selected so that the charge in the heteropolyoxometalate is zero. To achieve this, the number and/or charge of the cations A can be varied and/or by one or more further cations, for example selected from ammonium (NH)4 +) Alkali metal ion (e.g. Li)+、Na+、K+、Rb+、Cs+) And alkaline earth metal ions (e.g. Be)2+、Mg2 +、Ca2+、Sr2+、Ba2+) To balance the charge.
Furthermore, the heteropolyoxometalate anion may contain neutral ligands, such as H2O, thereby producing, for example, An[AlMn(H2O)W11O30]The structure of (1).
In a preferred embodiment of the invention, in the heteropolyoxometalates, the quaternary ammonium cation is of formula (VI), the quaternary phosphonium cation is of formula (VII), and the tertiary sulfonium cation is of formula (VIII):
R1R2R3R4N+(VI)
R1R2R3R4P+(VII)
R1R2R3S+(VIII)
wherein the residue R1、R2、R3And R4Independently selected from the group consisting of C1 to C80 hydrocarbons and polymers, and optionally, a residue R1、R2、R3And (if present) R4At least two of which are part of a ring or form a ring together with a nitrogen, phosphorus or sulfur atom.
These cations have antimicrobial properties, contribute to the antimicrobial properties of the entire heteropolyoxometalate material, and contribute to its ability to reduce biofilm growth on the surface of a substrate in or on a household appliance.
The presence of quaternary ammonium cations of formula (VI), quaternary phosphonium cations of formula (VII), or tertiary sulfonium cations of formula (VIII) also renders the heteropolyoxometalates described herein poorly or even insoluble in water. Preferably, the heteropolyoxometalates used in the present invention have a solubility in water of less than 10mg/l, preferably less than 1mg/ml, more preferably less than 0.1mg/ml, especially less than 0.01mg/ml at 20 ℃.
The lower solubility or even insolubility for aqueous liquids also contributes to the long-term efficacy of the heteropolyoxometalates as described herein, which relates to the reduction of biofilm growth and antimicrobial activity on the surface of component parts in or on household appliances, as they do not wash out of component parts used in household appliances over time when exposed to water or moisture.
The C1 to C80 hydrocarbons include branched or straight chain, saturated or unsaturated, substituted or unsubstituted alkyl, aryl or heteroaryl groups. Thus, these residues may also be waxes or waxes.
Examples of these C1 to C80 hydrocarbons include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl, C30, C64 alkyl, C65 alkyl, C66 alkyl, C67 alkyl, C68 alkyl, C69 alkyl, C70 alkyl, C71 alkyl, C72 alkyl, C73 alkyl, C74 alkyl, C75 alkyl, C75 alkyl, C76 alkyl, C77 alkyl, C78 alkyl, C79 alkyl, and C80 alkyl residue. These C1 to C80 hydrocarbons are preferably straight chain.
Preferred are C1 to C60 hydrocarbons including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl, C30 alkyl, C31 alkyl, C32 alkyl, C33 alkyl, C34 alkyl, C35 alkyl, C36 alkyl, C. These C1 to C60 hydrocarbons are preferably straight chain.
More preferred are C1 to C40 hydrocarbons including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl, C30 alkyl, C31 alkyl, C32 alkyl, C33 alkyl, C34 alkyl, C35 alkyl, C36 alkyl, C37 alkyl, C39 alkyl and C40 alkyl residues. These C1 to C40 hydrocarbons are preferably straight chain.
More preferred are C1 to C30 hydrocarbons including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, C25 alkyl, C26 alkyl, C27 alkyl, C28 alkyl, C29 alkyl and C30 alkyl residues. These C1 to C30 hydrocarbons are preferably straight chain.
More preferred are C2 to C25 hydrocarbons including ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, and C25 alkyl residues. These C2 to C25 are preferably linear.
Particularly preferred are C4 to C20 hydrocarbons including butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl residues. These C4 to C20 hydrocarbons are preferably straight chain.
In general, more preferably, R1、R2、R3And (if present) R4Is a hydrocarbon having at least four carbons, such as butyl, pentyl, hexyl, and the like, and even more preferably at least five carbon atoms. More preferably, R1、R2、R3And (if present) R4At least two of which are hydrocarbons having at least 4 carbons, such as butyl, pentyl, hexyl, and the like.
Suitable polymers include, for example, polymers comprising cationic side chains, such as phosphine-containing cationic poly (styrene) polymers, hydroxyl exchange membranes comprising quaternary ammonium hydroxide or quaternary phosphonium hydroxide functionality, poly (vinylamine) derivatives as described, for example, in EP 0580078 a1, polymeric phosphine ionomers as described, for example, in WO 94/10214, poly (alkyl-and aryl) p-phenoxy-benzenesulfonates, poly (acrylamide-co-diallyl-dimethylammonium), and poly (diallyldimethylammonium).
The ring formed with the nitrogen, phosphorus or sulfur atom may, for example, be a three-, four-, five-, six-or seven-membered ring, which may be saturated or unsaturated, and may contain one or more further heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur atoms. If the ring is unsaturated and if a double bond is present at the nitrogen, phosphorus or sulfonium cation of the ammonium, phosphine or sulfonium cationOn the sulfur atom, then R1、R2、R3Or R4One of which may not be present. Examples of suitable rings include aziridinium (azidinium), thiiranium (thiiranium), azetidinium (azetidinium), thienylium (thienium), pyrrolidinium (pyrolidinium), tetrahydrothiophenium (tetrahydrothiophenium), pyrrolinium (pyrolidinium), pyrolidinium (pyrolidinium), thiopyranium (thiopyrylium), hexamethyleneiminium (hexamethyleneimine), hexamethylenesulfonium (hexamethylenesulfonium), azonium (azothidium), azonium (azothidiazium), thiocycloheptathiotriene (thiothidiazium), pyrazolium (pyrazolylium), imidazolium (azonium), benzimidazolium (benzimidazolium), pyrazolium (pyrazolium), imidazolinium (indolinium), thiazolinium (pyrazolinium), thiazolinium (indolinium), thiazolinium (thiazolinium), thiazolinium (indolinium (thiazolinium), thiazolinium (thiazolium), thiazolium (thiazolinium), thiazolium (thiazolium), thiazolinium), thiazolium (thiazolinium), thiazolium), thiazolinium), thiazolium (thiazolium), thiazolium (thiazolinium), thiazolium (thiazolium), thiazolinium), thiazolium (thiazolium), thiazolium (thiazolium), thiazolium, Oxazolidines (oxazolidines), oxazolidinones (oxazolidones), guanine derivatives (guanine derivatives), cytosine derivatives (cytosine derivatives), adenine derivatives (adenine derivatives), thymine derivatives (thymine derivatives), cyclic amino acid and peptide derivatives (cyclic amino-acid and peptide derivatives), cyclic biguanide derivatives (cyclic biguanidine derivatives), cyclic guanidine derivatives (cyclic guanidine derivatives), and phosphorus analogs of these ring systems.
The rings may be substituted by one or more hydrocarbon residues, in particular C1 to C12 alkyl or aryl (in particular phenyl), preferably C1 to C6 alkyl residues. Suitable ring-containing cations are, for example, 1-butyl-3-methylimidazolium (1-butyl-3-methylimidazolium), 1-butyl-2, 3-dimethylimidazolium (1-butyl-2, 3-dimethylimidazolium), 1-methyl-3-octylimidazolium (1-methyl-3-octylimidazolium), 1-hexadecyl-3-methylimidazolium (1-hexadecyl-3-methylimidazolium), 1,3-didecyl-3-methylimidazolium (1,3-didecyl-3-methylimidazolium), and 1-benzyl-3-methylimidazolium (1-benzyl-3-methylimidazolium).
Preferred quaternary ammonium cations are the cations tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, tetranonylammonium, tetradecylammonium, tetradodecylammonium, tetratridecylammonium, tetratetradecylammonium, tetrapentadecylammonium, methyltributylammonium, methyltripetylammonium, methyltrihexylammonium, methyltriheptylammonium, methyltrioctylammonium, methyltrisinylammonium, methyltridecylammonium, methyltrienylammonium, methyltridedecylammonium, methyltridecylammonium, tributylhexylammonium, tributylheptylammonium, tributyloctylamine, tributylnonylamine, tributyldecylamine, tributylundecylammonium, tributyldodecylammonium, tributyltridecylammonium, tetramethylammonium, tetramethyltridecylammonium, tetramethylammonium, tetrabutylammonium, tetrabutylphosphonium, and mixtures, Tributyltetradecylammonium, tributylpentadecylammonium, tributylhexadecylammonium, trihexyltetradecylammonium and trihexylhexadecylammonium, in particular tetrabutylammonium cation, tetrahexylammonium cation, methyltrioctylammonium cation, tributyltetradecylammonium cation.
Preferred quaternary phosphine cations are the cations tetrapropylphosphine, tetrabutylphosphine, tetrapentylphosphine, tetrahexylphosphine, tetraheptylphosphine, tetraoctylphosphine, tetranonylphosphine, tetradecylphosphine, tetraundecylphosphine, tetradodecylphosphine, tetratridecylphosphine, tetratetradecylphosphine, methyltrioctylphosphine, tributyltetradecylphosphine, tributyldodecylphosphine, trihexyltetradecylphosphine, trihexylhexadecylphosphine, tetrahexylphosphine, methyltributylphosphine, methyltripetylphosphine, methyltrihexylphosphine, methyltriheptylphosphine, methyltrietonylphosphine, methyltrideylphosphine, tributylpentylphosphine, tributylhexylphosphine, tributylheptylphosphine, tributyloctylphosphine, tributylnonylphosphine, tributyldecylphosphine, tributylundecylphosphine, tributyldodecylphosphine, tributyltridecylphosphine, tetrabutylphosphonium, and the like, Tributyltetradecylphosphine, tributylpentadecylphosphine, tributylhexadecylphosphine, trihexylheptylphosphine, trihexyloctylphosphine, trihexylnonylphosphine, trihexyldecylphosphine, trihexylundecylphosphine, trihexdodecylphosphine, trihexyltridedecylphosphine, trihexyltetradecylphosphine, trihexylpentadecylphosphine and trihexylhexadecylphosphine.
Preferred tertiary sulfonium cations are, for example, tributylsulfonium cation, tripentylsulfonium cation, trihexylsulfonium cation, triheptylsulfonium cation, trioctylsulfonium cation, methyldioctylsulfonium cation and dibutyltetradecylsulfonium cation, especially tributylsulfonium cation and trihexylsulfonium cation.
Other suitable ammonium, phosphonium and sulfonium cations and their preparation are known in the art.
In a preferred embodiment of the present invention, in the heteropolyoxometalates, a comprises at least one cation selected from the group consisting of quaternary ammonium cations and quaternary phosphonium cations.
Particularly preferred heteropolyoxometalates are, for example:
heteropolyoxometalates based on the formula (I): [ (CH)3(CH2)3)4N]5[SiVW11O40]、[(CH3(CH2)3)4N]6[SiV2W10O40]、[(CH3(CH2)3)3P(Cl4H29)]5[SiVW11O40]、[(CH3(CH2)3)3P(Cl4H29)]6[SiV2Wl0O40]、[(CH3(CH2)3)3P(Cl4H29)]7[SiV3W9O40]、[(CH3(CH2)3)3P(Cl4H29)]8[SiV4W8O40]、[(CH3(CH2)3)3P(Cl4H29)]8[SiV4Mo8O40]、[(CH3(CH2)7)4N]5[SiVMo11O40]、[(CH3(CH2)7)3N(CH3)]6[SiV2Mo10O40]、[(CH3(CH2)3)3P((CH2)13CH3)]7[SiV3Mo9O40]、[(CH3(CH2)3)4N]11[PV8Mo4O40]、[(CH3(CH2)7)3N(CH3)]5[PCOW11O39]、[(CH3(CH2)3)3P((CH2)13CH3)]6[AlVW11O40]、[(CH3(CH2)3)4N]5[SiVW10MoO40]、[(CH3(CH2)3)3P(C14H29)]9[PV6Mo6O40]、[(CH3(CH2)3)3P(C14H29)]8[PV5Mo7O40]；
Heteropolyoxometalates based on the formula (II): [ (CH)3(CH2)3)4N]7[PW6O24]、[(CH3(CH2)7)4N]7[PMo6O24]、[(CH3(CH2)7)3N(CH3)]8[SiW6O24]、[(CH3(CH2)3)3P((CH2)13CH3)]8[SiMo6O24]、[(CH3(CH2)3)4N]9[AlW6O24]、[(CH3(CH2)3)4N]9[AlMo6O24]、[(CH3(CH2)5)4N]20[SiW4O24]、[(CH3(CH2)7)4N]20[SiMo4O24]、[(CH3(CH2)7)3N(CH3)]21[AlW4O24]、[(CH3(CH2)3)3P((CH2)13CH3)]21[AlMo4O24]；
Heteropolyoxometalates based on the formula (III): [ (CH)3(CH2)3)4N]2[W6O19]And [ (CH)3(CH2)3)3P((CH2)13CH3)]2[M6O19]；
Heteropolyoxometalates based on the formula (IV): [ (CH)3(CH2)7)3N(CH3)]8[Si2W18O62]、[(CH3(CH2)3)3P((CH2)13CH3)]8[Si2Mo18O62]；
Heteropolyoxometalates based on the formula (V): [ (CH)3(CH2)3)4N]15[P5W30O110]、[(CH3(CH2)7)3N(CH3)]20[Si5W30O110]、[(CH3(CH2)5)4N]15[P5MO30O110]、[(CH3(CH2)5)4N]20[Si5Mo30O110]。
A household appliance is preferred, wherein A is selected from one or more than two selected from the group consisting of (XR)1R2R3R4)+A cation of the group consisting of cations, wherein the radical R1、R2、R3And R4Is a substituted or unsubstituted alkyl, alkoxyalkyl (alkyloxoalkyl) or cycloalkyl group which may contain at least one heteroatom selected from O, S, N or P.
Preferably, the group R1、R2、R3And R4Has at least five carbon atoms, even more preferably at least eight carbon atoms. Preferably, X is selected from nitrogen or phosphorus.
Particularly preferred cations are methyltrioctylammonium and tributyltetradecylphosphine cation.
In the heteropolyoxometalates described herein, a "heteroatom" is phosphorus, silicon, germanium, aluminum or boron. If phosphorus, silicon, germanium, aluminum or boron is not included, the term "polyoxometallate" applies to the name of the substance.
However, as used herein, the term "polyoxometalate" is generally used synonymously with the term "heteropolyoxometalate" due to the usual presence of heteroatoms.
All heteropolyoxometalates described herein have molybdenum or tungsten oxide subunits, which may be partially replaced with titanium, vanadium, manganese, iron, cobalt, nickel or chromium oxide subunits.
The heteropolyoxometalates of formulae (I), (II), (III), (IV) and (V) and subformulae thereof as described herein can be prepared according to known methods.
The member portion comprises a polymer. I.e. it may comprise one or more than two polymers. In a preferred embodiment of the inventive household appliance, the component part comprises a thermoplastic, an elastomer, a thermoplastic elastomer, a duroplast or a mixture thereof.
As used herein, the term "thermoplastic" refers to a polymer that becomes pliable or moldable above a particular temperature and solidifies upon cooling. Examples of thermoplastic polymers include, but are not limited to, polyacrylates, acrylonitrile-butadiene-styrene, polyamides such as nylon, polyacetic acid, polybenzimidazole, polycarbonate, polyethersulfone, polyetheretherketone, polyetherimide, polyethylene, polyphenylene ether, polyphenylene sulfide, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polyurethane, polyester, and polytetrafluoroethylene (e.g., teflon).
As used herein, the term "elastomer" refers to a polymer that is viscoelastic (both viscous and elastic). Examples of elastomers include, but are not limited to, unsaturated rubbers such as natural polyisoprene (natural rubber), synthetic polyisoprene, polybutadiene, neoprene, butyl rubber, styrene-butadiene rubber, (hydrogenated) nitrile rubber, saturated rubbers such as ethylene propylene rubber, ethylene propylene diene monomer rubber, epichlorohydrin rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, fluoroelastomers and perfluoroelastomers, and ethylene-vinyl acetate.
As used herein, the term "thermoplastic elastomer" refers to a class of copolymers or physical mixtures of polymers composed of materials having both thermoplastic and elastomeric properties. Examples of thermoplastic elastomers include, but are not limited to, styrenic block copolymers, polyolefin blends, elastomeric alloys, thermoplastic polyurethanes, thermoplastic copolyesters, and thermoplastic polyamides.
As used herein, the term "rigid plastic" refers to a polymer that is no longer bendable after curing. Examples of duroplastics include, but are not limited to, aminoplasts, phenolics, epoxies, polyacrylates, polyurethanes, polyesters, urea-formaldehyde resins, melamine-formaldehyde resins, and phenol-formaldehyde resins.
In a more preferred embodiment of the invention, the component part of the household appliance comprises a polymer selected from the group consisting of polypropylene, polyethylene terephthalate, other polyesters, polyamides, polyurethanes, polyacrylates, polycarbonates, polystyrenes, polyimides, polymethacrylates, polyoxyolefins, polyphenylene ethers, polyvinyl esters, polyvinyl ethers, polyvinylidene chloride, acrylonitrile-butadiene-styrene, natural and synthetic polyisoprenes, polybutadiene, neoprene, styrene-butadiene rubber, tetrafluoroethylene, silicone resins, acrylate resins, polyurethane resins, silicone resins, polyester resins, alkyd resins, epoxy resins, phenolic resins and urea or amine based resins or mixtures thereof.
More preferably, the polymer is at least a thermoplastic polymer selected from the group consisting of polypropylene, polyethylene and styrene copolymers. Even more preferably, the thermoplastic polymer is polypropylene.
In the component part of the household appliance of the present invention, it is preferable that the polyoxometalate is contained in the surface layer having a thickness of 0.01 to 0.5 mm. Further, it is preferable that the polyoxometallate content of the surface layer is in the range of 1 to 50 wt% based on the weight of the surface layer. In the present invention, the polyoxometallate is anchored to a silica-containing matrix. However, with regard to the content of polyoxometallate mentioned above, it is usual to refer to unanchored polyoxometallate as a reference.
For example, activation of the polypropylene surface can be accomplished by using plasma. The methyl group of polypropylene can be converted into an oxidized group (ketone, aldehyde, carboxylic acid, etc.) using plasma in an oxidizing atmosphere, and then easily used as an anchor point.
In a preferred embodiment of the household appliance, the polyoxometallate anchored to the silica-containing substrate can be obtained by:
(a) reacting a polyoxometalate with an alkoxy or chlorosilane to form an alkoxysilane-anchored polyoxometalate;
(b) hydrolyzing the alkoxysilane-anchored polyoxometalate obtained in step (a) with an aqueous liquid; and
(c) reacting the hydrolyzed alkoxysilane-anchored polyoxometalate obtained in step (b) with a silica-containing substrate.
Preferably, the polyoxometallate is reacted in step (a) with a compound of formula Si (OR)1)2R2 2In which R is1Is alkyl and R2Is OR1Or Cl. R1Preference is given to alkyl chains having up to five carbon atoms, such as methyl or ethyl.
Furthermore, the invention relates to a process for the manufacture of polyoxometallate anchored on a silica-containing substrate, the process comprising the steps of:
(a) reacting a polyoxometalate with an alkoxy or chlorosilane to form an alkoxysilane-anchored polyoxometalate;
(b) hydrolyzing the alkoxysilane-anchored polyoxometalate obtained in step (a) with an aqueous liquid; and
(c) reacting the hydrolyzed alkoxysilane-anchored polyoxometalate obtained in step (b) with a silica-containing substrate.
In a preferred process, the polyoxometallate is reacted in step (a) with a compound of the formula Si (OR)1)2R2 2In which R is1Is alkyl, R2Is OR1Or Cl. R1Preference is given to alkyl chains having up to five carbon atoms, such as methyl or ethyl.
Furthermore, the invention relates to a process for producing a component part of a domestic appliance, comprising a thermoplastic polymer and a polyoxometalate, wherein the process comprises the following steps:
(i) mixing at least one thermoplastic polymer with a silica-containing matrix anchored to a polyoxometalate; and
(ii) (ii) injection moulding the mixture obtained in step (i) to form the component.
Furthermore, the invention relates to an alternative process for manufacturing a component part of a household appliance comprising a thermoplastic polymer and a polyoxometalate, wherein the process comprises the following steps:
(j) mixing at least one thermoplastic polymer with a silica-containing matrix;
(jj) injection molding the mixture obtained in step (j);
(jjj) contacting the shaped product obtained in step (jj) with a polyoxometalate;
(jjjj) performing a grafting reaction between the silica-containing substrate and the polyoxometalate to form the building block.
Thus, for the manufacture of the component parts of the inventive household appliance, there are various possibilities for introducing the anchored polyoxometallate. This is particularly true when thermoplastic polymers are used as the polymer.
The incorporation of the generally used heteropolyoxometalates into the polymer bulk can be achieved, for example, by mixing the anchored heteropolyoxometalates with the polymer in order to obtain a dispersion or compound of heteropolyoxometalates and polymer. The dispersion or compound may then be subjected to injection molding or extrusion, for example, to form the desired component part.
However, the anchored heteropolyoxometalate may be mixed with the monomer before the polymerization is carried out. After polymerization, the resulting polymer may, for example, be subjected to compounding processes, pressureless processing techniques (e.g., casting, dip coating, foaming) or compression molding, rolling and calendering, extrusion, blow molding or injection molding processes or drawing, thermoforming or printing to form the desired component part.
In the household appliance of the invention, the anchored polyoxometallate may be used in a component part, for example in a reservoir, together with a polymeric organic or inorganic binder. Preferably, the optional adhesive is selected from the group consisting of acrylate-based adhesives, polyurethane-based adhesives, and silicone-based adhesives.
Suitable acrylate-based adhesives are, for example, those from
Of a company
2K-acrylic, WorleCryl A1220 from WorlE Chemie, Inc., Covestro, Inc
A145, water-reducible hydroxy-functional polyacrylate dispersions and polyacrylate dispersions from the Covestro company
A265 BA. A suitable Polyurethane (PUR) based adhesive is, for example, ATCOAT Atrepur 340 from ATCOAT company. Suitable silicone-based adhesives are, for example, those from Evonik corporation
EF. 2577 LowVoc from Dow Corning Corp or fromBluesil RES 991 from Bluesil corporation.
In the manufacture of the household appliance according to the invention, the desired component parts may be obtained, for example, by dip-coating the corresponding polymer bodies into a liquid containing the binder and the anchored polyoxometalate.
Furthermore, it is also possible to produce foils in which the anchored polyoxometalate is combined with a suitable support material and binder, so that only a relatively small amount of polyoxometalate may be required to cover a large surface area. Such a foil may be applied, for example, by gluing or melt bonding. Furthermore, such a foil can be placed directly in an injection mould and thus be used directly for manufacturing the component part.
The invention has several advantages. In a household appliance, polyoxometallates for the component parts due to their antimicrobial properties can be introduced into the household appliance in an improved manner. Less polyoxometallate is required to obtain a component part with the same antimicrobial efficiency. Furthermore, other adverse side effects occurring upon degradation of the polyoxometallate, such as unwanted color changes, can be avoided. The operating costs of the manufacturing process can be reduced, since less polyoxometallate is required for manufacturing the component parts having the same biocidal effect. In embodiments of the present invention, it is even possible to avoid any thermal or chemical degradation of the polyoxometalate. Furthermore, more and sometimes even all active sites with antimicrobial properties will be available compared to known processes and household appliances.
In addition, the invention also has the following advantages: a household appliance with improved hygiene can be obtained in a simple and cost-effective manner. In particular, this is advantageous in the case of water-conducting household appliances, which have a significantly reduced sensitivity to dirt, in particular with regard to microorganisms.
Particular advantages of using the anchored polyoxometallates described herein are: anchored polyoxometallates are capable of functioning as catalytic systems for years without additional activation or energy input. Therefore, oxygen radicals that sterilize the inside of the home appliance can be easily and continuously generated. In order to keep the polyoxometalate on the surface of the component part and prevent dissolution into the surrounding liquid or gaseous medium or any other consumption due to contact with the surrounding medium, it is preferred to use the preferred specific cations described herein. Organic ions having long chains are particularly suitable, as described herein. Particularly preferred examples thereof are methyltrioctylammonium (methyltrioctyllyammonium) and tributyltetradecylphosphine (tributylenetetradecylphosphonium) cations.
Drawings
Hereinafter, the present invention will be described in more detail by referring to examples and fig. 1 to 3.
Fig. 1 is a schematic view of relevant parts of one embodiment of a household appliance according to the invention configured as a washing machine, as a non-limiting example.
Figure 2 is a representation of an atomic model of a polyoxometalate which has been provided with a silicon-containing linker to facilitate subsequent anchoring of the polyoxometalate to a silica-containing substrate.
Fig. 3 shows, by means of an atomic model, the different steps of a process for producing polyoxometallate that has been grafted, i.e. anchored, on a flat silica-containing substrate, for example a glass sheet.
Detailed Description
Examples of the invention
These examples illustrate the use for the manufacture of a composition comprising polypropylene as polymer and at least one polyoxometallate K8[α-SiW11O39]The component parts of the household appliance. The polymer made of polypropylene used is not of a specific shape and inorganic cations are used, but this is sufficient for illustrative purposes.
Preparation of Polyoxometallate (POM) functionalized by silicon anchorable groups.
K8[α-SiW11O39]13H2Synthesis of O
11[WO4]2-+[SiO3]2-+16H+->[α-SiW11O39]8-+8H2O
Solution A: sodium metasilicate (11g, 50mmol) was dissolved in 100ml of water.
Solution B: sodium tungstate (182g, 0.55mol) was dissolved in 300ml of boiling water in a separate 1L beaker equipped with a magnetic stir bar.
Then 165ml of 4M HCl was added slowly to solution B over 10 minutes with vigorous stirring. Solution a was then poured into the tungstate solution and the pH was quickly adjusted to between 5 and 6 by the addition of 4M HCl solution (50 mL). The resulting solution was boiled for 1 hour and then cooled to room temperature. The pH was maintained for 100 minutes by the addition of a small amount of 4M HCl. Solid potassium chloride (150g) was then added to the solution and gently stirred. After a period of time, the white solid was collected by filtration through a sintered glass funnel. Washed with 2X 50mL of cold water and finally dried in air.
K8[α-SiW11O39]Functionalization of
Under vigorous stirring to K8[α-SiW11O39](1.25×10-3mol) in 100ml of H2Solution in O4.76 mol (Si (OR) was added dropwise1)2R2 2，1R ═ alkyl chains, such as ethyl; r2＝O1R or Cl). The reaction mixture was left until the formed emulsion disappeared. The pH was adjusted to 1 using 1M HCl. The reaction mixture was stirred overnight or until the solution became colorless. The solvent was removed in vacuo to give a white solid. The functionalized K obtained8[α-SiW11O39]Can be represented by the atomic model of fig. 2, where the polyoxometalate has been provided with a silicon-containing linker to facilitate later anchoring of the polyoxometalate on the silica-containing matrix.
Example 1
Anchored to polypropylene (PP) added with 10% by weight of Pyrosil (silica)
A suspension of functionalized POM and sample with added PP (10: 1 by weight) in wet toluene was stirred at 100 ℃ overnight. Thereafter, the PP samples were washed successively with toluene, dimethyl chloride and diethyl ether and characterized by XPS.
Example 2
Anchored to polypropylene (PP) supplemented with 10 wt% hollow glass microspheres IM16K and glass fibers
The functionalized POM and the sample with added PP (10: 1 by weight) were left without stirring in a suspension in wet hexane, isopropanol or ethanol for 5 minutes under laboratory standard temperature conditions (about 24 ℃). The PP samples were then washed with the same solvent as used, i.e. hexane or isopropanol or ethanol, to remove the not yet anchored molecules, then dried and characterized with XPS.
Thus, in examples 1 and 2, a polypropylene-based polymer body is used, wherein the polypropylene is present in a mixture with a silica-containing matrix, but said silica-containing matrix is different in both examples. Anchoring of the polyoxometalate is then achieved by contacting the polymer body with a suspension of wet, i.e. aqueous, functionalized POM.
Fig. 1 is a schematic view of relevant parts of one embodiment of a household appliance according to the invention configured as a washing machine, as a non-limiting example.
The washing machine 1 of the present embodiment has a tub 2, and a drum 3 is rotatably mounted in the tub 2 and may be driven by a driving motor 15. For ergonomic reasons, the axis of rotation 4 of the drum 3 is oriented at a small angle upwards away from the horizontal plane, in order to make it easier to access and inspect the interior of the drum 3. By this arrangement, in cooperation with the laundry agitator 5 and the scooping means 6 for the washing liquid 7 which are specially formed at the inner surface of the drum jacket, an enhancement of the flow of the washing liquid 7 through the laundry 8 can be achieved.
The washing machine 1 also has a water supply system comprising a water connection fixture for the domestic water supply 9, an electrically controlled valve 10 and a water supply pipe 11 extending to the outer tub 2 and supplied via a detergent dispenser box 12, the supplied liquid being able to transport the detergent portion from said detergent dispenser box 12 to the outer tub 2.
A heating device 14 is also provided in the outer tub 2. The valve 10 and the heating device 14 can be controlled by the program control system 13 according to a program execution plan, which can be linked to a time program and/or to the attainment of specific measured values of parameters within the laundry washing machine 1, such as the liquid level, the liquid temperature, the rotation speed of the drum 3, etc. 16 denotes a pump for liquid in the outer tub 2, in particular washing liquid 7.
The reservoir 18 can store greywater that has been used for rinsing the laundry 8. The grey water may be used for a later wash cycle. To this end, the reservoir 18 is connected via a line ("feed pipe for rinsing liquid") 19 to the valve 10, which also regulates the fresh water supply. A circulation element 20 and an air inlet element 21, which can also be controlled by the program control system 13, are provided in the reservoir 18. By these measures, a particularly efficient oxidation reaction can be carried out in the reservoir 18 at the inner surface 17.
In the particular washing machine 1, which is an exemplary embodiment of the household appliance according to the invention, the component parts comprising the polymer and the at least one polyoxometalate anchored on the silica-containing matrix are the detergent dispenser box 12 and the water reservoir 18. Anchored polyoxometallates are present in particular in the respective inner surfaces 17.
FIG. 2 is a schematic representation of an atomic model of a polyoxometalate which has been prepared by reacting a polyoxometalate with a compound of the formula Si (OR)4Wherein R is an alkyl group, to facilitate later anchoring of the polyoxometalate on the silica-containing substrate.
Fig. 3 shows, by means of an atomic model, the different steps of a process for producing polyoxometallate that has been grafted, i.e. anchored, on a flat silica-containing substrate, for example a glass sheet. TEOS means tetraethyl orthosilicate.
List of reference numerals
Household appliance, household appliance running with water and washing machine
2 (outer) barrel
3 Drum for washing articles
4 axis of rotation of the drum
5 washing agitator
6 scooping device
7 washing liquid
8 washing article
9 domestic water supply
10 valve
11 water supply pipe
12 detergent dispenser box, component parts
13 program control system
14 heating device
15 driving motor
16 pump
17 interior surfaces containing polyoxometallate
18 water reservoir, component part
19 feed pipe for rinse water
20 circulation element
21 air intake element
Claims (15)
1. A household appliance (1) having a component part (12, 18) comprising a polymer and at least one polyoxometalate, characterized in that the polyoxometalate is anchored on a silica-containing matrix.
2. The household appliance (1) according to claim 1, wherein said silica-containing matrix is selected from the group consisting of silica minerals, aluminosilicate minerals and glass.
3. The household appliance (1) according to claim 2, wherein said aluminosilicate mineral is a zeolite.
4. The household appliance (1) according to claim 2, wherein said glass is in the form of hollow glass beads or glass fibers.
5. The household appliance (1) according to any one of claims 1 to 4, wherein said at least one polyoxometalate is a heteropolyoxometalate of formula (I), (II), (III), (IV) and/or (V):
[An]m+[XMqZr-q-oZ’oOs]m-(I)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
r is 11 or 12, and r is a linear or linear,
o is 0 or 1, or a combination thereof,
s-37, 38, 39 or 40,
when r is 11, q is 0, 1, 2,3, 4, 5, 6, 7, 8 or 9,
when r is 12, q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9 or 10;
[An]m+[XMqZt-q-oZ’oO24]m-(II)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
t is 4 or 6, and the total weight of the product,
o is 0 or 1, or a combination thereof,
when t is 6, q is 0, 1, 2,3 or 4,
when t is 4, q is 0, 1 or 2, and
q is 1, 2 or 3 when t ═ 4 and X ═ P;
[An]m+[XpMqZ6-q-p-oZ’oO19]m-(III),
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
p is 0 or 1, and
q is 0, 1, 2 or 3;
[An]m+[X2MqZ18-q-oZ’oO62]m-(IV)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and
q is 1, 2 or 3 when X ═ P;
[An]m+[X5MqZ30-q-oZ’oO110]m-(V)，
wherein the content of the first and second substances,
m-is the negative charge of the heteropolyoxometalate anion,
m + is the positive charge of the cation A,
|m-|＝|m+|，
n is the number of cations A required to provide a positive charge m +,
z and Z' are independently selected from W and Mo,
x is selected from P, Si, Ge, Al and B,
m is selected from Ti, V, Mn, Fe, Co, Ni, Zn and Cr,
o is 0 or 1, or a combination thereof,
q is 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27;
and wherein A is selected from one or two or more cations and comprises at least one cation selected from the group consisting of quaternary ammonium cations, quaternary phosphonium cations and tertiary sulfonium cations.
6. The household appliance (1) according to claim 5, wherein the polyoxometalate is a heteropolyoxometalate of formulae (I), (II), (III), (IV) and (V), wherein Z ═ W.
7. Household appliance (1) according to claim 5 or 6, wherein A is selected from the group consisting of (XR)1R2R3R4)+A cation, wherein the group R1、R2、R3And R4Is a substituted or unsubstituted alkyl, alkyl-oxoalkyl or cycloalkyl group capable of containing at least one heteroatom selected from O, S, N or P.
8. Household appliance (1) according to claim 7, wherein the group R1、R2、R3And R4Has at least five carbon atoms, more preferably at least eight carbon atoms.
9. Household appliance (1) according to any of claims 1 to 8, wherein said polymer is at least a thermoplastic polymer selected from the group consisting of polypropylene, polyethylene and styrene copolymers.
10. The household appliance (1) according to any of claims 1 to 9, wherein said polyoxometalate is contained in a surface layer (17) having a thickness of 0.01 to 0.5 mm.
11. The household appliance (1) according to claim 10, wherein the polyoxometalate content of the surface layer (17) is in the range of 1 to 50 wt%, based on the weight of the surface layer (17).
12. The household appliance (1) according to any one of claims 1 to 11, wherein the polyoxometalate anchored to the silica-containing matrix is obtainable by:
(a) reacting a polyoxometalate with an alkoxy or chlorosilane to form an alkoxysilane-anchored polyoxometalate;
(b) hydrolyzing the alkoxysilane-anchored polyoxometalate obtained in step (a) with an aqueous liquid; and
(c) reacting the hydrolyzed alkoxysilane-anchored polyoxometalate obtained in step (b) with a silica-containing substrate.
13. A process for the manufacture of polyoxometallates anchored to a silica-containing substrate comprising the following steps
(a) Reacting a polyoxometalate with an alkoxy or chlorosilane to form an alkoxysilane-anchored polyoxometalate;
(b) hydrolyzing the alkoxysilane-anchored polyoxometalate obtained in step (a) with an aqueous liquid; and
(c) reacting the hydrolyzed alkoxysilane-anchored polyoxometalate obtained in step (b) with a silica-containing substrate.
14. A process for manufacturing a component part (12, 18) of a household appliance (1) comprising a polymer and at least one polyoxometalate, wherein the process comprises the steps of:
(i) mixing at least one thermoplastic polymer with a silica-containing matrix anchored to a polyoxometalate; and
(ii) injection molding the mixture obtained in step (a) to form the member.
15. A process for manufacturing a component part (12, 18) of a household appliance (1) comprising a polymer and at least one polyoxometalate, wherein the process comprises the steps of:
(j) mixing at least one thermoplastic polymer with a silica-containing matrix;
(jj) injection molding the mixture obtained in step (j);
(jjj) contacting the shaped product obtained in step (jj) with a polyoxometalate;
(jjjj) performing a grafting reaction between the silica-containing substrate and the polyoxometalate to form the building block.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| EP17382627.2 | 2017-09-20 | ||
| ES201731135 | 2017-09-20 | ||
| EP17382627.2A EP3459423B1 (en) | 2017-09-20 | 2017-09-20 | Household appliance with an anchored polyoxometalate containing component part, process for the manufacture of an anchored polyoxometalate and processes for the manufacture of the component part |
| ESP201731135 | 2017-09-20 | ||
| PCT/EP2018/074003 WO2019057507A1 (en) | 2017-09-20 | 2018-09-06 | Household appliance with an anchored polyoxometalate containing component part, process for the manufacture of the polyoxometalate and processes for the manufacture of the component part |
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| CN111093457A true CN111093457A (en) | 2020-05-01 |
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